Polymer-containing organo-metal catalysts

Abstract

The invention relates to polymer-containing catalysts (e.g., polymer-containing organo-metal catalysts) that may be useful in various applications (e.g., polymerization of macrocyclic oligoesters). Advantages of these catalysts include the improved ability to prepare, store, and handle the catalyst in open air; higher molar volume and molecular weight; and the ability to produce a blend of reactants and a catalyst (e.g., a macrocyclic oligoester and a polymerization catalyst) for subsequent one-step reaction (e.g., polymerization of macrocyclic oligoesters).

What is claimed is:  
     
       1. A method for polymerizing a macrocyclic oligoester comprising a structural repeat unit of the formula                    
       where A is an alkylene, a cycloalkylene, or a mono- or polyoxyalkylene group; and B is a divalent aromatic or alicyclic group, the method comprising the step of contacting, at an elevated temperature, a macrocyclic oligoester and a polymerization catalyst, the polymerization catalyst comprising a compound having the molecular formula. 
       
         
           (R 1 —Y 1 —) i -M(-Y 2 R 2 ) j ,  
         
       
       wherein: 
       each of i and j is an integer; i≧0; j≧1;  
       each R 1  independently is, or two or more R 1  groups taken together are, an alkyl group or an alkyl ether group each having between 1 and 20 carbon atoms;  
       each R 2  independently is a polymeric group comprising 25 or more carbon atoms, wherein at least one R 2  comprises at least one of (i) a polyalkylene group comprising 25 or more carbon atoms and (ii) a polyether group;  
       each Y 1  and Y 2  independently is a single bond or a heteroatom selected from the group consisting of O, S, and N; and  
       M is Ti, Sn, or —Z 1 -(X) k -Z 2 -, wherein Z 1  independently is Ti or Sn, Z 2  independently is Ti or Sn, each X independently is O or O—R 3 —O, wherein R 3  is an alkylene group, and k is 1, 2, or 3  
     
     
       2. The method of  claim 1  wherein the polymerization catalyst comprises a polyalkylene group. 
     
     
       3. The method of  claim 1  wherein the macrocyclic oligoester and the polymerization catalyst are components of a blend material. 
     
     
       4. A method for polymerizing a macrocyclic oligoester comprising the steps of 
       (a) providing a molten macrocyclic oligoester, wherein the macrocyclic oligoester comprises a structural repeat unit of the formula                    
       where A is an alkylene, a cycloalkylene or a mono- or polyoxyalkylene group; and B is a divalent aromatic or alicyclic group; 
       (b) providing a molten polymerization catalyst, the polymerization catalyst comprising a compound having the molecular formula; and  
       
         
           (R 1 —Y 1 —) i -MY 2 —R 2 ) j ,  
         
       
       wherein: 
       each of i and j is an integer; i≧0; j≧1;  
       each R 1  independently is, or two or more R 1  groups taken together are, an alkyl group or an alkyl ether group each having between 1 and 20 carbon atoms;  
       each R 2  independently is a polymeric group comprising 25 or more carbon atoms, wherein at least one R 2  comprises at least one of (i) a polyalkylene group comprising 25 or more carbon atoms and (ii) a polyether group;  
       each Y 1  and Y 2  independently is a single bond or a heteroatom selected from the group consisting of O, S, and N; and  
       M is Ti, Sn, or -Z 1 -(X) k -Z 2 -, wherein Z 1  independently is Ti or Sn, Z 2  independently is Ti or Sn, each X independently is O or O—R 3 —O, wherein R 3  is an alkylene group, and k is 1, 2, or 3; and  
       (c) contacting the molten macrocyclic oligoester and the molten polymerization catalyst, thereby causing polymerization of the macrocyclic oligoester.  
     
     
       5. The method of  claim 4  wherein the contacting step (c) takes place in a mold. 
     
     
       6. A method for polymerizing a macrocyclic oligoester comprising the steps of 
       (a) providing a molten macrocyclic oligoester in a mixing chamber, wherein the macrocyclic oligoester comprises a structural repeat unit of the formula                    
       where A is an alkylene, a cycloalkylene or a mono- or polyoxyalkylene group; and B is a divalent aromatic or alicyclic group; 
       (b) providing a molten polymerization catalyst in the mixing chamber; the polymerization catalyst comprising a compound having the molecular formula;  
       
         
           (R 1 —Y 1 —) i -M-(-Y 2 —R 2 ) j ,  
         
       
       wherein: 
       each of i and j is an integer; i≧0; j≧1;  
       each R 1  independently is, or two or more R 1  groups taken together are, an alkyl group or an alkyl ether group each having between 1 and 20 carbon atoms;  
       each R 2  independently is a polymeric group comprising 25 or more carbon atoms, wherein at least one R 2  comprises at least one of (i) a polyalkylene group comprising 25 or more carbon atoms and (ii) a polyether group;  
       each Y 1  and Y 2  independently is a single bond or a heteroatom selected from the group consisting of O, S, and N; and  
       M is Ti, Sn, or -Z 1 -(X) k -Z 2 -, wherein Z 1  independently is Ti or Sn, Z 2  independently is Ti or Sn, each X independently is O or O—R 3 —O, wherein R 3  is an alkylene group, and is 1, 2, or 3;  
       (c) mixing the molten macrocyclic oligoester and molten polymerization catalyst in the mixing chamber; and  
       (d) introducing a mixed molten macrocyclic oligoester and polymerization catalyst into a mold.